CN102666596A - Processes for preparation of cyclic acyclic diene copolymer and rubber composition - Google Patents

Processes for preparation of cyclic acyclic diene copolymer and rubber composition Download PDF

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CN102666596A
CN102666596A CN2010800536292A CN201080053629A CN102666596A CN 102666596 A CN102666596 A CN 102666596A CN 2010800536292 A CN2010800536292 A CN 2010800536292A CN 201080053629 A CN201080053629 A CN 201080053629A CN 102666596 A CN102666596 A CN 102666596A
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nickel
acid
neodymium
aluminium
group
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CN102666596B (en
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秦增全
铃木英寿
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Bridgestone Corp
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Bridgestone Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
    • C08F4/80—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from iron group metals or platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F232/02—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings
    • C08F232/06—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings having two or more carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/52—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from boron, aluminium, gallium, indium, thallium or rare earths
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/057—Metal alcoholates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T152/00—Resilient tires and wheels
    • Y10T152/10—Tires, resilient
    • Y10T152/10495—Pneumatic tire or inner tube

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerization Catalysts (AREA)

Abstract

A process for preparing a copolymer of an acyclic conjugated diene and a cyclic conjugated diene using a polymerization catalyst system comprising a transition metal compound or a lanthanide metal compound, an alkylating agent, and an inorganic halide alcoholate, and rubber compositions and tires comprising the same. The copolymer contains at least 90% acyclic conjugated diene monomer, has a number average molecular weight of between 40,000 and 300,000, and has a cis-bond content of at least 92%.

Description

The preparation method of ring-type and acyclic dienes multipolymer and rubber combination
Technical field
One or more embodiments of the application relate to the method for the multipolymer that utilizes transition metal or lanthanide series metal catalyst composition to prepare ring-type and acyclic conjugate diene monomer and introduce the rubber combination of this multipolymer.
Summary of the invention
The application describes to use and comprises (a) transistion metal compound or lanthanide metal compound; (b) alkylating agent and (c) polymerisation catalyst system of inorganic halides alcoholate prepare the method for the multipolymer of at least a acyclic conjugated diolefine and at least a cyclic conjugated diene; Wherein said multipolymer comprises at least 90% acyclic conjugate diene monomer, has 40,000 to 300; 000 number-average molecular weight, and have at least 92% cis linkage content.In addition, in one or more embodiments, the application describes at least a multipolymer of processing through foregoing method comprise 30phr at least and less than the rubber combination of at least a rubber compounding thing of 70phr.
In one or more embodiments; The application further describes and comprises at least a multipolymer that contains at least a cyclic conjugated diene monomer and at least a acyclic conjugate diene monomer and the rubber combination of at least a rubber compounding thing; Wherein said at least a multipolymer comprises at least 90% acyclic conjugate diene monomer, has 50,000 to 150; 000 number-average molecular weight, and have at least 92% cis linkage content.
In one or more embodiments; The application further describes the pneumatic tyre that comprises tread package, inside and outside sidewall components and housing unit, and at least a assembly that wherein is selected from the group of being made up of inside and outside sidewall components and housing unit comprises through the multipolymer like method preparation described herein.
Embodiment
According to one or more embodiments of describing among the application; At least a acyclic conjugate diene monomer and at least a cyclic conjugated diene monomer can use the polymerisation catalyst system polymerization; Thereby form and have 40; The multipolymer of 000 to 300,000 number-average molecular weight, at least 90% acyclic conjugate diene monomer content and at least 92% cis-1,4 linkage content; Said polymerisation catalyst system comprises: (a) transistion metal compound or lanthanide metal compound, (b) alkylating agent and (c) inorganic halides alcoholate.
The instance of at least a acyclic conjugate diene monomer includes, but not limited to 1,3-butadiene, isoprene, 1; 3-pentadiene, 1,3-hexadiene, 2,3-dimethyl--1; 3-divinyl, 2-ethyl-l, 3-divinyl, 2-methyl isophthalic acid, 3-pentadiene, 3-methyl isophthalic acid; 3-pentadiene, 4-methyl isophthalic acid, 3-pentadiene and 2,4-hexadiene.Can in copolymerization, use the mixture of two or more conjugated diolefines.
The instance of at least a cyclic conjugated diene monomer includes, but not limited to 1,1,1,3-cycloheptadiene and 1,3-cyclooctadiene, and verivate.
Any specific lanthanide metal compound that the enforcement of one or more embodiments described herein is not limited to use in the catalyst system or the selection of transistion metal compound.
In one or more embodiments, catalyst system can comprise lanthanide metal compound or transistion metal compound, alkylating agent and comprise the halogen contained compound of unstable halogen atom more than.Comprise the occasion of unstable halogen atom more than at lanthanide metal compound or transistion metal compound and/or alkylating agent, catalyst system need not comprise independent halogen contained compound; For example, catalyst system can only comprise halogenated lanthanon or transistion metal compound and alkylating agent.In some embodiments, alkylating agent can comprise aikyiaiurnirsoxan beta and at least a other organo-aluminium compound the two.In another other embodiment; The compound that comprises non-coordination anion; Or non-coordination anion precursor promptly can carry out chemical reaction to form the compound of non-coordination anion, and the halogen contained compound that can replace comprising unstable halogen atom more than uses.In these or other embodiment, except the above-mentioned composition or component that illustrates, can also use other organometallic compound, Lewis base and/or catalyst modifier.For example, disclosed in 813 as at USP 6,699 in one embodiment, can use nickel compound containing as molecular weight regulator, be introduced into for referencial use at this.
Various lanthanide metal compounds or transistion metal compound or its mixture can be used for catalyst system.In one or more embodiments, these compounds can be dissolved in varsol such as aromatic hydrocarbon, aliphatic hydrocrbon or clicyclic hydrocarbon.In other embodiments, can in polymerisation medium, suspend with the insoluble lanthanon of hydrocarbon or the transistion metal compound that form catalytic active substance also is available.
The available lanthanide metal compound can comprise the atom of at least a lanthanum, neodymium, cerium, praseodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium and didymium in the catalyst system.Didymium can comprise the mixture that is purchased by the REE of monazite sand acquisition.Preferably, can use lanthanum, samarium or neodymium compound.
Group of the lanthanides atom in one or more lanthanide metal compounds can be in various oxidation state, include but not limited to 0 ,+2 ,+3 and+4 oxidation state.Lanthanide compound includes but not limited to, lanthanon carboxylate salt, lanthanon organophosphate, lanthanon organic phosphonate, lanthanon organic secondary phosphine acid salt (organophosphinate), lanthanon carbaminate, lanthanon MGD, lanthanon xanthogenate, lanthanon beta-diketon hydrochlorate (lanthanide beta-diketonate), alkoxide or fragrant lanthanum trioxide series elements, lanthanide halides, the false halogenide of lanthanon, zirconyl oxyhalides lanthanon and organolanthanide.
The term organolanthanide refers to comprise any lanthanide compound of at least one lanthanon-carbon bond.These compounds mainly are to comprise those of cyclopentadienyl moiety (Cp), substituted cyclopentadienyl moiety, allyl group and substituted allyl group part, but do not get rid of other.The organolanthanide that is fit to comprises Cp 3Ln, Cp 2LnR, Cp 2LnCl, CpLnCl 2, CpLn (cyclooctatetraene), (C 5Me 5) 2LnR, LnR 3, Ln (allyl group) 3, and Ln (allyl group) 2Cl, wherein Ln representes that group of the lanthanides atom and R represent alkyl.
Not expecting to limit under the situation of method enforcement disclosed herein, below discuss and concentrate on neodymium compound, but those skilled in the art can select similar lanthanide metal compound based on other lanthanide metals.Useful neodymium compound includes but not limited to, carboxylic acid neodymium, organic phosphoric acid neodymium, organic phospho acid neodymium, organic phospho acid neodymium, carboxylamine neodymium, dithiocarbamic acid neodymium, xanthogenic acid neodymium, beta-diketon acid neodymium, alkoxide neodymium, fragrant Neodymium trioxide, halogenation neodymium, false halogenation neodymium and zirconyl oxyhalides neodymium.
Available carboxylic acid neodymium includes but not limited in the catalyst system disclosed herein, formic acid neodymium, neodymium acetate, vinylformic acid neodymium, methylacrylic acid neodymium, valeric acid neodymium, glucono-neodymium, Hydrocerol A neodymium, fumaric acid neodymium, lactic acid neodymium, toxilic acid neodymium, neodymium oxalate, 2 ethyl hexanoic acid neodymium, neodecanoic acid neodymium (having another name called the tertiary monocarboxylic acid neodymium), neodymium naphthenate, Triple Pressed Stearic Acid neodymium, oleic acid neodymium, phenylformic acid neodymium and VPP neodymium.
Available organic phosphoric acid neodymium includes but not limited in the catalyst system disclosed herein, dibutylphosphoric acid neodymium, the basic neodymium phosphate of DAP neodymium, two, diheptyl neodymium phosphate, dioctyl neodymium phosphate, two (1-methylheptyl) neodymium phosphate, two (2-ethylhexyl) neodymium phosphate, didecyl neodymium phosphate, two-dodecylphosphoric acid neodymium, two-octadecyl neodymium phosphate, two oleyl neodymium phosphates, xenyl neodymium phosphate, two (right-the nonyl phenyl) neodymium phosphate, butyl (2-ethylhexyl) neodymium phosphate, (1-methylheptyl) (2-ethylhexyl) neodymium phosphate and (2-ethylhexyl) (right-the nonyl phenyl) neodymium phosphate.
Available organic phospho acid neodymium includes but not limited in the catalyst system disclosed herein, butyl phosphonic acids neodymium, amyl group phosphonic acids neodymium, hexyl phosphonic acids neodymium, heptyl phosphonic acids neodymium, octyl phosphonic acid neodymium, (1-methylheptyl) phosphonic acids neodymium, (2-ethylhexyl) phosphonic acids neodymium, decylphosphonic acid neodymium, dodecyl phosphonic acids neodymium, octadecyl phosphonic acids neodymium, oleyl phosphonic acids neodymium, phenyl-phosphonic acid neodymium, (right-the nonyl phenyl) phosphonic acids neodymium, butyl butyl phosphonic acids neodymium, amyl group amyl group phosphonic acids neodymium, hexyl hexyl phosphonic acids neodymium, heptyl heptyl phosphonic acids neodymium, octyl group octyl group neodymium phosphate, (1-methylheptyl) (1-methylheptyl) phosphonic acids neodymium, (2-ethylhexyl) (2-ethylhexyl) phosphonic acids neodymium, decyl decylphosphonic acid neodymium, dodecyl dodecyl phosphonic acids neodymium, octadecyl octadecyl phosphonic acids neodymium, oleyl oleyl phosphonic acids neodymium, phenyl phosphonic acids neodymium, (right-the nonyl phenyl) (right-the nonyl phenyl) phosphonic acids neodymium, butyl (2-ethylhexyl) phosphonic acids neodymium, (2-ethylhexyl) butyl phosphonic acids neodymium, (1-methylheptyl) (2-ethylhexyl) phosphonic acids neodymium, (2-ethylhexyl) (1-methylheptyl) phosphonic acids neodymium, (2-ethylhexyl) (right-the nonyl phenyl) phosphonic acids neodymium and (right-the nonyl phenyl) (2-ethylhexyl) phosphonic acids neodymium.
The organic phospho acid neodymium of available includes but not limited in the catalyst system disclosed herein, butyl phospho acid neodymium, amyl group phospho acid neodymium, ethylhexyl hypophosphorous acid neodymium, heptyl phospho acid neodymium, octyl group phospho acid neodymium, (1-methylheptyl) phospho acid neodymium, (2-ethylhexyl) phospho acid neodymium, decyl phospho acid neodymium, dodecyl phospho acid neodymium, octadecyl phospho acid neodymium, oleyl phospho acid neodymium, phenyl phosphinic acid neodymium, (right-the nonyl phenyl) phospho acid neodymium, dibutyl phospho acid neodymium, diamyl phospho acid neodymium, dihexyl phospho acid neodymium, diheptyl phospho acid neodymium, dioctylphosphinic acid(HDOP) neodymium, two (1-methylheptyl) phospho acid neodymium, two (2-ethylhexyl) phospho acid neodymium, didecyl phospho acid neodymium, two-dodecyl phospho acid neodymium, two-octadecyl phospho acid neodymium, two oleyl phospho acid neodymiums, diphenyl phosphonic acid neodymium, two (right-the nonyl phenyl) phospho acid neodymium, butyl (2-ethylhexyl) phospho acid neodymium, (1-methylheptyl) (2-ethylhexyl) phospho acid neodymium and (2-ethylhexyl) (right-the nonyl phenyl) phospho acid neodymium.
Available carboxylamine neodymium includes but not limited in the catalyst system disclosed herein, dimethylamino formic acid neodymium, diethylamino formic acid neodymium, diisopropylaminoethyl formic acid neodymium, dibutylamino formic acid neodymium and dibenzyl amino formic acid neodymium.
Available dithiocarbamic acid neodymium includes but not limited in the catalyst system disclosed herein, and dimethyl dithiocarbamic acid neodymium, diethyldithiocar bamic acid neodymium, diisopropyl disulfide are for carboxylamine neodymium, dibutyl dithiocaarbamate neodymium and dibenzyl aminodithioformic acid neodymium.
Available xanthogenic acid neodymium includes but not limited in the catalyst system disclosed herein, p-dimethylamino-azo-benzene ortho acid neodymium, xanthogenic acid neodymium, isopropyl xanthan acid neodymium, butyl xanthic acid neodymium and benzyl xanthogenic acid neodymium.
Available beta-diketon acid neodymium includes but not limited in the catalyst system disclosed herein, Acetyl Acetone acid neodymium, trifluoroacetyl group pyruvic acid neodymium, hexafluoro Acetyl Acetone acid neodymium, benzoyl-pyruvic acid neodymium and 2,2,6,6-tetramethyl--3,5-heptane two ketone acid neodymiums.
Available alkoxide or fragrant Neodymium trioxide include but not limited in the catalyst system disclosed herein, methyl alcohol neodymium, ethanol neodymium, Virahol neodymium, 2-Ethylhexyl Alcohol neodymium, phenol neodymium, nonylphenol neodymium and naphthols neodymium.
Available halogenation neodymium includes but not limited in the catalyst system disclosed herein, neodymium fluoride, Neodymium trichloride, neodymium bromide and neodymium iodide.
The false halogenation neodymium of available includes but not limited to cyaniding neodymium, cyanic acid neodymium, sulfocyanic acid neodymium, nitrine neodymium and ferrocyanide neodymium in the catalyst system disclosed herein.
Available zirconyl oxyhalides neodymium includes but not limited in the catalyst system disclosed herein, neodymium oxide fluoride, neodymium oxychloride and bromine Neodymium trioxide.Comprise that at halogenation neodymium, zirconyl oxyhalides neodymium or other neodymium compound under the occasion of unstable halogen atom more than, catalyst system need not comprise independent halogen contained compound.Lewis base such as THF (THF) can be used as the dissolution aids of this type neodymium compound in inert organic solvents and use.
The available transistion metal compound can comprise from first or at least a atom of second series transition metal in the catalyst system.Preferably, can use the compound of nickel, cobalt or palladium.In some embodiments, transistion metal compound comprises nickel compound containing.
Transition metal atoms in the transistion metal compound can be in various oxidation state, include but not limited to 0 ,+2 ,+3 and+4 oxidation state.Transistion metal compound includes but not limited to that metal carboxylate, carboxylate metal borate, metal organophosphate, metal organic phosphonate, metal organic secondary phosphine acid salt, metal amino formate, metal dithionite are for carbaminate, metal xanthogenate, metal beta-diketon hydrochlorate, metal alkoxide or fragrant oxide compound, metal halide, the false halogenide of metal, metal oxyhalogenide and organometallic compound.
Not expecting to limit under the situation of method enforcement disclosed herein, below discuss and concentrate on nickel compound, but those skilled in the art can select similar compound based on other transition metal.Useful nickel compound includes but not limited to, nickel carboxylate, carboxylic acid nickelous borate, organic phosphoric acid nickel, organic phospho acid nickel, organic phospho acid nickel, carboxylamine nickel, dithiocarbamic acid nickel, xanthogenic acid nickel, beta-diketon acid nickel, alkoxide nickel, fragrant nickel oxide, nickel halogenide, false nickel halogenide, zirconyl oxyhalides nickel and organic nickel compound.
The available nickel carboxylate includes but not limited in the catalyst system disclosed herein, nickel formate, nickelous acetate, vinylformic acid nickel, methylacrylic acid nickel, valeric acid nickel, gluconic acid nickel, Hydrocerol A nickel, fumaric acid nickel, lactic acid nickel, toxilic acid nickel, nickelous oxalate, 2 ethyl hexanoic acid nickel, neodecanoic acid nickel, nickel naphthenate, nickel stearate, oleic acid nickel, nickel benzoate and VPP nickel.
Available carboxylic acid nickelous borate includes but not limited in the catalyst system disclosed herein, through type (RCOONiO) 3B or (RCOONiO) 2The compound of B (OR) definition, each R that wherein can be identical or different is Wasserstoffatoms or unit price organic group.In one embodiment; Each R can be alkyl; Such as but not limited to, alkyl, naphthenic base, substituted naphthenic base, alkenyl, cycloalkenyl group, substituted cycloalkenyl group, aryl, substituted aryl, aralkyl, alkaryl, allyl group and alkynyl, wherein each group preferably comprises 1 carbon atom; Perhaps form the carbon atom of the suitable minimum quantity of this group, until 20 carbon atoms.These alkyl can comprise heteroatoms, such as but not limited to, nitrogen, oxygen, silicon, sulphur and phosphorus atom.The carboxylic acid nickelous borate can comprise USP 4,522, and those disclosed in 988 is introduced into for referencial use at this.The specific examples of carboxylic acid nickelous borate comprises neodecanoic acid nickelous borate (II), caproic acid nickelous borate (II), naphthenic acid nickelous borate (II), Triple Pressed Stearic Acid nickelous borate (II), sad nickelous borate (II), 2 ethyl hexanoic acid nickelous borate (II) and its mixture.
Available organic phosphoric acid nickel includes but not limited in the catalyst system disclosed herein, dibutylphosphoric acid nickel, the basic nickelous phosphate of DAP nickel, two, diheptyl nickelous phosphate, dioctyl nickelous phosphate, two (1-methylheptyl) nickelous phosphate, two (2-ethylhexyl) nickelous phosphate, didecyl nickelous phosphate, two-dodecylphosphoric acid nickel, two-octadecyl nickelous phosphate, two oleyl nickelous phosphates, xenyl nickelous phosphate, two (right-the nonyl phenyl) nickelous phosphate, butyl (2-ethylhexyl) nickelous phosphate, (1-methylheptyl) (2-ethylhexyl) nickelous phosphate and (2-ethylhexyl) (right-the nonyl phenyl) nickelous phosphate.
Available organic phospho acid nickel includes but not limited in the catalyst system disclosed herein, butyl phosphonic acids nickel, amyl group phosphonic acids nickel, hexyl phosphonic acids nickel, heptyl phosphonic acids nickel, octyl phosphonic acid nickel, (1-methylheptyl) phosphonic acids nickel, (2-ethylhexyl) phosphonic acids nickel, decylphosphonic acid nickel, dodecyl phosphonic acids nickel, octadecyl phosphonic acids nickel, oleyl phosphonic acids nickel, phenyl-phosphonic acid nickel, (right-the nonyl phenyl) phosphonic acids nickel, butyl butyl phosphonic acids nickel, amyl group amyl group phosphonic acids nickel, hexyl hexyl phosphonic acids nickel, heptyl heptyl phosphonic acids nickel, octyl group octyl group nickelous phosphate, (1-methylheptyl) (1-methylheptyl) phosphonic acids nickel, (2-ethylhexyl) (2-ethylhexyl) phosphonic acids nickel, decyl decylphosphonic acid nickel, dodecyl dodecyl phosphonic acids nickel, octadecyl octadecyl phosphonic acids nickel, oleyl oleyl phosphonic acids nickel, phenyl phosphonic acids nickel, (right-the nonyl phenyl) (right-the nonyl phenyl) phosphonic acids nickel, butyl (2-ethylhexyl) phosphonic acids nickel, (2-ethylhexyl) butyl phosphonic acids nickel, (1-methylheptyl) (2-ethylhexyl) phosphonic acids nickel, (2-ethylhexyl) (1-methylheptyl) phosphonic acids nickel, (2-ethylhexyl) (right-the nonyl phenyl) phosphonic acids nickel and (right-the nonyl phenyl) (2-ethylhexyl) phosphonic acids nickel.
The organic phospho acid nickel of available includes but not limited in the catalyst system disclosed herein, butyl phospho acid nickel, amyl group phospho acid nickel, ethylhexyl hypophosphorous acid nickel, heptyl phospho acid nickel, octyl group phospho acid nickel, (1-methylheptyl) phospho acid nickel, (2-ethylhexyl) phospho acid nickel, decyl phospho acid nickel, dodecyl phospho acid nickel, octadecyl phospho acid nickel, oleyl phospho acid nickel, phenyl phosphinic acid nickel, (right-the nonyl phenyl) phospho acid nickel, dibutyl phospho acid nickel, diamyl phospho acid nickel, dihexyl phospho acid nickel, diheptyl phospho acid nickel, dioctylphosphinic acid(HDOP) nickel, two (1-methylheptyl) phospho acid nickel, two (2-ethylhexyl) phospho acid nickel, didecyl phospho acid nickel, two-dodecyl phospho acid nickel, two-octadecyl phospho acid nickel, two oleyl phospho acid nickel, diphenyl phosphonic acid nickel, two (right-the nonyl phenyl) phospho acid nickel, butyl (2-ethylhexyl) phospho acid nickel, (1-methylheptyl) (2-ethylhexyl) phospho acid nickel and (2-ethylhexyl) (right-the nonyl phenyl) phospho acid nickel.
Available carboxylamine nickel includes but not limited in the catalyst system disclosed herein, dimethylamino nickel formate, diethylamino formic acid nickel, diisopropylaminoethyl nickel formate, dibutylamino nickel formate and dibenzyl amino nickel formate.
Available dithiocarbamic acid nickel includes but not limited in the catalyst system disclosed herein, and nickel dimethyldithiocarbamate, nickel diethyldithiocarbamate, diisopropyl disulfide are for carboxylamine nickel, nickel dibutyl dithiocarbamate and dibenzyl aminodithioformic acid nickel.
Available xanthogenic acid nickel includes but not limited in the catalyst system disclosed herein, p-dimethylamino-azo-benzene ortho acid nickel, nickel ethyl xanthate, nickel isopropyl xanthate, butyl xanthic acid nickel and benzyl xanthogenic acid nickel.
Available beta-diketon acid nickel includes but not limited to nickel acetylacetonate, trifluoroacetyl group pyruvic acid nickel, hexafluoro nickel acetylacetonate, benzoyl-pyruvic acid nickel and 2,2,6,6-tetramethyl--3,5-heptane two ketone acid nickel in the catalyst system disclosed herein.
Available alkoxide or fragrant nickel oxide include but not limited in the catalyst system disclosed herein, methyl alcohol nickel, ethanol nickel, Virahol nickel, 2-Ethylhexyl Alcohol nickel, phenol nickel, nonylphenol nickel and naphthols nickel.
The available nickel halogenide includes but not limited in the catalyst system disclosed herein, nickelous fluoride, nickelous chloride, nickelous bromide and nickelous iodide.
The false nickel halogenide of available includes but not limited to nickel cyanide, cyanic acid nickel, sulfocyanic acid nickel, nitrine nickel and ferrocyanide nickel in the catalyst system disclosed herein.
Available zirconyl oxyhalides nickel includes but not limited in the catalyst system disclosed herein, fluorine nickel oxide, oxychlorination nickel and bromine nickel oxide.Comprise that at nickel halogenide, zirconyl oxyhalides nickel or other nickel compound containing under the occasion of unstable halogen atom more than, catalyst system need not comprise independent halogen contained compound.The dissolution aids that Lewis base such as alcohol can be used as this compounds uses.
Term organic nickel compound refers to comprise any nickel compound of at least one nickel-carbon bond.Available organic nickel compound includes but not limited in the catalyst system disclosed herein; Two (cyclopentadienyl moiety) nickel (being also referred to as nickelocene), two (pentamethyl-cyclopentadienyl moiety) nickel (being also referred to as the decamethyl nickelocene), two (tetramethyl-ring pentadienyl) nickel, two (ethyl cyclopentadienyl moiety) nickel, two (sec.-propyl cyclopentadienyl moiety) nickel, two (pentadienyl) nickel, two (2; 4-dimethyl pentadiene base) nickel, (cyclopentadienyl moiety) (pentadienyl) nickel, two (1, the 5-cyclooctadiene) nickel, two (allyl group) nickel, two (methacrylic) nickel and two (crot(on)yl) nickel.
Can use various alkylating agents or its mixture.Available alkylating agent in the catalyst system disclosed herein (may also be referred to as the hydrocarbylation agent) includes but not limited to, can alkyl be transferred to the organometallic compound of another metal.Typically, these reagent comprise the organometallic compound of electropositive metal like the 1st, 2 and 3 family's metals (metal of IA, IIA and IIIA family).In one or more embodiments, alkylating agent comprises organoaluminum and organo-magnesium compound.Comprise at alkylating agent under the occasion of unstable halogen atom that alkylating agent also can be used as halogen contained compound.
Term " organo-aluminium compound " refers to contain any aluminum compound of at least one aluminium-carbon bond.In one or more embodiments, organo-aluminium compound dissolves in varsol.
In one or more embodiments, the available organo-aluminium compound includes but not limited in the catalyst system disclosed herein, by general formula AlR nX 3-nThe organo-aluminium compound of expression; Each R that wherein can be identical or different is the unit price organic group that is connected to the aluminium atom via carbon atom; Each X that wherein can be identical or different is Wasserstoffatoms, halogen atom, carboxylic acid ester groups, alkoxide group (alkoxide group) or fragrant oxide groups (aryloxide group), and wherein n is 1 to 3 integer.In one or more embodiments, each R can be an alkyl, such as but not limited to, alkyl, naphthenic base, substituted cycloalkyl, alkenyl, cycloalkenyl group, substituted cycloalkenyl, aryl, substituted aryl, aralkyl, alkaryl, allyl group and alkynyl.These alkyl can contain heteroatoms, such as but not limited to, nitrogen, oxygen, boron, silicon, sulphur and phosphorus atom.
The available organo-aluminium compound includes but not limited in the catalyst system disclosed herein, trialkyl aluminium, hydrogenation dialkyl aluminium, dihydro alkyl aluminium, dialkyl aluminium carboxylate salt, alkyl aluminium two (carboxylate salt), alkoxide dialkyl aluminium, dioxane oxidation alkyl aluminium, halogenation dialkyl aluminium, dihalide alkyl aluminium, fragrant oxidation dialkyl aluminium and two fragrant oxidation hydrocarbyl aluminium compounds.
The available tri alkyl aluminum compound includes but not limited in the catalyst system disclosed herein; Trimethylaluminium, triethyl aluminum, triisobutyl aluminium, tri-n-n-propyl aluminum, triisopropylaluminiuand, three n-butylaluminum, tri-tert aluminium, three n-pentyl aluminium, three neo-pentyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, three (2-ethylhexyl) aluminium, thricyclohexyl aluminium, three (1-methylcyclopentyl) aluminium, triphenyl aluminum, three p-methylphenyl aluminium, three (2, the 6-3,5-dimethylphenyl) aluminium, tribenzyl aluminium, diethylammonium phenyl aluminium, diethylammonium p-methylphenyl aluminium, diethylammonium benzyl aluminium, ethyl phenylbenzene aluminium, ethyl di-p-tolyl aluminium and ethyl dibenzyl aluminium.
Available hydrogenation dialkyl aluminum compound includes but not limited in the catalyst system disclosed herein, diethyl aluminium hydride, hydrogenation di aluminium, hydrogenation di-isopropyl aluminium, hydrogenation di-n-butyl aluminium, diisobutylaluminium hydride, hydrogenation di-n-octyl aluminium, hydrogenation phenylbenzene aluminium, hydrogenation di-p-tolyl aluminium, hydrogenation dibenzyl aluminium, hydrogenation phenyl aluminium triethyl, hydrogenation phenyl n-propyl aluminium, hydrogenation phenyl sec.-propyl aluminium, hydrogenation phenyl n-butylaluminum, hydrogenation phenyl aluminium isobutyl, hydrogenation phenyl octyl aluminum, hydrogenation p-methylphenyl aluminium triethyl, hydrogenation p-methylphenyl n-propyl aluminium, hydrogenation p-methylphenyl sec.-propyl aluminium, hydrogenation p-methylphenyl n-butylaluminum, hydrogenation p-methylphenyl aluminium isobutyl, hydrogenation p-methylphenyl octyl aluminum, hydrogenation benzyl aluminium triethyl, hydrogenation benzyl n-propyl aluminium, hydrogenation benzyl sec.-propyl aluminium, hydrogenation benzyl n-butylaluminum, hydrogenation benzyl aluminium isobutyl and hydrogenation benzyl octyl aluminum.
Available dihydro alkyl aluminium includes but not limited in the catalyst system disclosed herein, dibydroethyl aluminium, dihydro n-propyl aluminium, dihydro sec.-propyl aluminium, dihydro n-butylaluminum, dihydro aluminium isobutyl and dihydro octyl aluminum.
Available chlorination dialkyl aluminum compound includes but not limited in the catalyst system disclosed herein, diethylaluminum chloride, chlorination di aluminium, chlorination di-isopropyl aluminium, chlorination di-n-butyl aluminium, di-isobutyl aluminum chloride, chlorination di-n-octyl aluminium, diphenyl antimony chloride base aluminium, chlorination di-p-tolyl aluminium, chlorination dibenzyl aluminium, chlorination phenyl aluminium triethyl, chlorination phenyl n-propyl aluminium, chlorination phenyl sec.-propyl aluminium, chlorination phenyl n-butylaluminum, chlorination phenyl aluminium isobutyl, chlorination phenyl octyl aluminum, chlorination p-methylphenyl aluminium triethyl, chlorination p-methylphenyl n-propyl aluminium, chlorination p-methylphenyl sec.-propyl aluminium, chlorination p-methylphenyl n-butylaluminum, chlorination p-methylphenyl aluminium isobutyl, chlorination p-methylphenyl octyl aluminum, zephiran chloride aluminium triethyl, zephiran chloride n-propyl aluminium, zephiran chloride sec.-propyl aluminium, zephiran chloride n-butylaluminum, zephiran chloride aluminium isobutyl and zephiran chloride octyl aluminum.
Available dichloride alkyl aluminium includes but not limited in the catalyst system disclosed herein, ethylaluminium dichloride, dichloride n-propyl aluminium, dichloride sec.-propyl aluminium, dichloride n-butylaluminum, aluminium isobutyl dichloride and dichloride octyl aluminum.
Other organo-aluminium compound of available includes but not limited in the catalyst system disclosed herein; Caproic acid dimethyl-aluminium, sad diethyl aluminum, 2 ethyl hexanoic acid diisobutyl aluminum, neodecanoic acid dimethyl-aluminium, Triple Pressed Stearic Acid diethyl aluminum, oleic acid diisobutyl aluminum, aluminium trimethide two (hexanoate), aluminium triethyl two (octylate), aluminium isobutyl two (2-ethylhexoate), aluminium trimethide two (neodecanoate), aluminium triethyl two (stearate), aluminium isobutyl two (oleate), dimethyl-aluminium methylates, diethyl aluminum methylate, diisobutyl aluminum methylate, dimethyl-aluminium ethylate, diethyl aluminum ethylate, diisobutyl aluminum ethylate, dimethyl-aluminium phenolate, diethyl aluminum phenolate, diisobutyl aluminum phenolate, aluminium trimethide diformazan alkoxide, aluminium triethyl diformazan alkoxide, aluminium isobutyl diformazan alkoxide, aluminium trimethide diethylate, aluminium triethyl diethylate, aluminium isobutyl diethylate, aluminium trimethide hexichol phenates, aluminium triethyl hexichol phenates and aluminium isobutyl hexichol phenates etc., and composition thereof.
Another kind of organo-aluminium compound comprises aikyiaiurnirsoxan beta.The available aikyiaiurnirsoxan beta includes but not limited in the catalyst system disclosed herein, the oligomeric line style aikyiaiurnirsoxan beta that can be represented by following general formula:
Figure BDA00001686836800131
With the oligomeric cyclic aikyiaiurnirsoxan beta that can represent by following general formula:
Figure BDA00001686836800132
Wherein x can be the integer of 1-about 100, about in other embodiments 10-about 50; Y can be the integer of 2-about 100, about in other embodiments 3-about 20; Each R that wherein can be identical or different 1It can be the unit price organic group that is connected to the aluminium atom via carbon atom.In one or more embodiments, each R 1Be alkyl, such as but not limited to, alkyl, naphthenic base, substituted naphthenic base, alkenyl, cycloalkenyl group, substituted cycloalkenyl group, aryl, substituted aryl, aralkyl, alkaryl, allyl group and alkynyl.These alkyl can contain heteroatoms, such as but not limited to nitrogen, oxygen, boron, silicon, sulphur and phosphorus atom.The mole number that should be noted that the aikyiaiurnirsoxan beta that is used for the application refers to the mole number of aluminium atom rather than the mole number of oligomeric aikyiaiurnirsoxan beta molecule.This convention is used in the catalyst technical field of utilizing aikyiaiurnirsoxan beta usually.
Aikyiaiurnirsoxan beta can be passed through tri alkyl aluminum compound and water prepared in reaction.This reaction can be carried out according to known method; For example (1) wherein can be dissolved in tri alkyl aluminum compound in the organic solvent; The method that contacts with water then; (2) wherein tri alkyl aluminum compound can be contained in as the crystal water of metal-salt or be adsorbed in inorganic or organic cpds the water reaction method and (3) wherein tri alkyl aluminum compound can be present in will monomer polymerized or monomer solution in the method for water reaction.
The available aluminium alkoxide compound includes but not limited in the catalyst system disclosed herein; The MAO (MMAO) of MAO (MAO), modification, ethyl aikyiaiurnirsoxan beta, n-propyl aikyiaiurnirsoxan beta, sec.-propyl aikyiaiurnirsoxan beta, butyl aikyiaiurnirsoxan beta, isobutyl aluminium alkoxide, n-pentyl aikyiaiurnirsoxan beta, neo-pentyl aikyiaiurnirsoxan beta, n-hexyl aikyiaiurnirsoxan beta, n-octyl alumina alkane, 2-ethylhexyl aikyiaiurnirsoxan beta, cyclohexyl aikyiaiurnirsoxan beta, 1-methylcyclopentyl aikyiaiurnirsoxan beta, phenyl aikyiaiurnirsoxan beta and 2; 6-3,5-dimethylphenyl aikyiaiurnirsoxan beta etc., and composition thereof.Can be through using technology that these those skilled in the art know by using C 2-C 12Alkyl, preferably form the MAO of modification with the methyl of about 20-80% in the isobutyl-substituent methyl aikyiaiurnirsoxan beta.
Aikyiaiurnirsoxan beta can be used separately or with other organo-aluminium compound combination.In one embodiment, MAO and at least a other organo-aluminium compound (for example, AlR nX 3-n) like diisobutylaluminium hydride combination use.
As stated, the alkylating agent of catalyst system can comprise organo-magnesium compound.The term organo-magnesium compound refers to contain any magnesium compound of at least one magnesium-carbon bond.Organo-magnesium compound dissolves in varsol.Utilizable one type of organo-magnesium compound can be by formula MgR 2Expression, each R that wherein can be identical or different is the unit price organic group, condition is that this group is connected to magnesium atom via carbon atom.In one or more embodiments, each R can be an alkyl, and the gained organo-magnesium compound is the dialkyl magnesium compound.The instance of alkyl includes but not limited to, alkyl, naphthenic base, substituted naphthenic base, alkenyl, cycloalkenyl group, substituted cycloalkenyl group, aryl, allyl group, substituted aryl, aralkyl, alkaryl and alkynyl.These alkyl can contain heteroatoms, such as but not limited to nitrogen, oxygen, silicon, sulphur and phosphorus atom.
The instance of available dialkyl magnesium compound includes but not limited in the catalyst system disclosed herein, magnesium ethide, di magnesium, di-isopropyl magnesium, dibutylmagnesium, dihexyl magnesium, diphenyl magnesium, dibenzyl magnesium and composition thereof.
Utilizable another kind of organo-magnesium compound comprises those that can be represented by formula RMgX; Wherein R is the unit price organic group; Condition is that this group is connected to magnesium atom via carbon atom, and X is Wasserstoffatoms, halogen atom, carboxylic acid ester groups, alkoxide group or fragrant oxide groups.In one or more embodiments, R can be an alkyl, such as but not limited to alkyl, naphthenic base, substituted naphthenic base, alkenyl, cycloalkenyl group, substituted cycloalkenyl group, aryl, allyl group, substituted aryl, aralkyl, alkaryl and alkynyl.These alkyl can contain heteroatoms, such as but not limited to nitrogen, oxygen, boron, silicon, sulphur and phosphorus atom.In one or more embodiments, X is carboxylic acid ester groups, alkoxide group or fragrant oxide groups.
The exemplary types of the organo-magnesium compound that can be represented by formula RMgX includes but not limited to hydrogenation alkyl magnesium, halogenation alkyl magnesium, alkyl magnesium carboxylate salt, alkyl magnesium alkoxide, alkyl magnesium phenates and composition thereof.
The specific examples of the organo-magnesium compound that can be represented by formula RMgX comprises hydrogenation methyl magnesium, ethyl hydride magnesium, hydrogenation dibutyl magnesium, hydrogenation hexyl magnesium, hydrogenation phenyl magnesium, hydrogenation benzyl magnesium, methylmagnesium-chloride, ethyl-magnesium-chloride, butyl magnesium chloride, chlorination hexyl magnesium, phenylmagnesium chloride, benzyl magnesium chloride, methylmagnesium-bromide, ethyl-magnesium-bromide, butyl magnesium bromide, bromination hexyl magnesium, phenyl-magnesium-bromide, bromination benzyl magnesium, caproic acid methyl magnesium, caproic acid magnesium ethide, caproic acid dibutyl magnesium, caproic acid hexyl magnesium, caproic acid phenyl magnesium, caproic acid benzyl magnesium, methyl magnesium ethylate, magnesium ethide ethylate, dibutyl magnesium ethylate, hexyl magnesium ethylate, phenyl magnesium ethylate, benzyl magnesium ethylate, methyl magnesium phenolate, magnesium ethide phenolate, dibutyl magnesium phenolate, hexyl magnesium phenolate, phenyl magnesium phenolate and benzyl magnesium phenolate etc., and composition thereof.
The various halogen contained compounds or its mixture that contain unstable halogen atom more than can be used for catalyst system.The instance of halogen atom includes but not limited to, fluorine, chlorine, bromine and iodine.Also can two or more halogen contained compound combinations with similar and different halogen atom be used.In one or more embodiments, halogen contained compound dissolves in varsol.The insoluble halogen contained compound of hydrocarbon that can be suspended in the polymerisation medium to form catalytic active substance in other embodiments, is useful.
The suitable type of halogen contained compound includes but not limited to, halogen simple substance (elemental halogens), blended halogen, hydrogen halide, Organohalogen compounds, inorganic halides, inorganic halides alcoholate, metal halide, organo-metallic halogenide and composition thereof.
Available halogen simple substance includes but not limited in the catalyst system disclosed herein, fluorine, chlorine, bromine and iodine.
Available blended halogen includes but not limited in the catalyst system disclosed herein, single iodine chloride, single iodine bromide IBr, iodine trichloride and iodine pentafluoride.
The available hydrogen halide includes but not limited in the catalyst system disclosed herein, hydrogen fluoride, hydrogenchloride, hydrogen bromide and hydrogen iodide.
The available Organohalogen compounds include but not limited in the catalyst system disclosed herein, tertiary butyl chloride, tert.-butyl bromide, chlorallylene, allyl bromide 98, benzyl chloride, bromotoluene, chloro-ditan, bromo-ditan, trityl group chlorine, trityl group bromine, benzal base muriate, benzal base bromide, METHYL TRICHLORO SILANE, phenyl-trichloro-silicane, dimethyldichlorosilane(DMCS), diphenyl dichlorosilane, trimethylchlorosilane, Benzoyl chloride 99min., benzoyl bromide, propionyl chloride, PROPIONYL CHLORIDE, methyl chlorocarbonate and bromo methyl-formiate.
The available inorganic halides includes but not limited in the catalyst system disclosed herein, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, bromine phosphorus oxide, boron trifluoride, boron trichloride, boron tribromide, silicon tetrafluoride, silicon tetrachloride, Silicon bromide, silicon tetraiodide, fuming liquid arsenic, arsenous bromide, arsenous iodide, selenic chloride, selenium tetrabromide, tellurium tetrachloride, tellurium tetrabromide and tellurium tetraiodide.
Available inorganic halides alcoholate includes but not limited in the catalyst system disclosed herein, the boron trifluoride alcoholate, and wherein alcoholate partly comprises 4-20 carbon atom.
The available metal halide includes but not limited in the catalyst system disclosed herein, tin tetrachloride, tin tetrabromide, aluminum chloride, alchlor, butter of antimony, antimony pentachloride, antimony tribro-, aluminium triiodide, aluminum trifluoride, gallium trichloride, tribromide gallium, triiodide gallium, three gallium fluorides, Indium-111 chloride, indium tribromide, indium triiodide, indium trifluoride, titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, zinc dichloride, dibrominated zinc, two zinc iodides and bifluoride zinc.
Available organo-metallic halogenide includes but not limited in the catalyst system disclosed herein, chlorodimethylalumiu, diethylaluminum chloride, bromination dimethyl-aluminium, bromination diethyl aluminum, fluoridize dimethyl-aluminium, fluoridize diethyl aluminum, methylaluminium dichloride, ethylaluminium dichloride, dibrominated aluminium trimethide, dibrominated aluminium triethyl, bifluoride aluminium trimethide, bifluoride aluminium triethyl, sesquialter methyl chloride aluminium, sesquialter ethylaluminium chloride, sesquialter chlorination aluminium isobutyl, methylmagnesium-chloride, methylmagnesium-bromide, iodate methyl magnesium, ethyl-magnesium-chloride, ethyl-magnesium-bromide, butyl magnesium chloride, butyl magnesium bromide, phenylmagnesium chloride, phenyl-magnesium-bromide, benzyl magnesium chloride, trimethyltin chloride, trimethyl tin bromide, triethyltin chloride, bromination triethyltin, dichloride two-tertiary butyl tin, dibrominated-two-tertiary butyl tin, dichloride dibutyl tin, dibrominated dibutyl tin, tributyltin chloride and bromination tributyl tin.
As stated; In some embodiments; The compound that contains non-coordination anion, or non-coordination anion precursor promptly can carry out chemical reaction to form the compound of non-coordination anion, and the halogen contained compound that can replace comprising unstable halogen atom more than uses.The compound that contains non-coordination anion is well known in the art.Usually, non-coordination anion is because sterically hindered and do not form the big negatively charged ion of spatial volume of co-ordination bond with the active site of for example catalyst system.Exemplary coordination anion comprises four aryl boric acid salt anionics and fluoridizes four aryl boric acid salt anionics.The compound that contains non-coordination anion also comprises counter cation such as carbon, ammonium or phosphorus positively charged ion.Exemplary counter cation comprises triaryl carbocation and N, N-dialkyl aniline positively charged ion (N, N-dialkylanilinium cations).The examples for compounds that contains non-coordination anion and counter cation comprises triphenylcarbenium four (pentafluorophenyl group) borate, N; Accelerine four (pentafluorophenyl group) borate, triphenylcarbenium four [3; Two (trifluoromethyl) phenyl of 5-] borate and N; Accelerine four [3, two (trifluoromethyl) phenyl of 5-] borate.
Non-coordination anion precursor is included in the compound that can form non-coordination anion under the reaction conditions.Exemplary non-coordination anion precursor comprises triarylboron BR 3, wherein R is strong electrophilic aryl such as pentafluorophenyl group or 3, two (trifluoromethyl) phenyl of 5-.
Aforementioned catalyst system can have high catalytic activity to conjugated-diolefin (co) polymer being combined into the stereotaxis polydiene in the wide region of catalyst concn and catalyst component ratio.Think that catalyst component can interact to form active catalyst species.Also think the concentration that possibly depend on other catalyst component for the optimum concn of any catalyst component.
In one or more embodiments; The mol ratio of alkylating agent and lanthanon or transistion metal compound (alkylating agent/metal) can about 1: 1-about 1; 000: 1, about in other embodiments 2: about 500: 1 of 1-and about in other embodiments 5: 1-changed in about 200: 1.
In using aikyiaiurnirsoxan beta and the two those embodiment of at least a other organoaluminum reagent as alkylating agent; The mol ratio of aikyiaiurnirsoxan beta and lanthanon or transistion metal compound (aikyiaiurnirsoxan beta/metal) can about 5: 1-about 1; 000: 1, about in other embodiments 10: about 700: 1 of 1-and about in other embodiments 20: 1-changed in about 500: 1; The mol ratio of at least a other organo-aluminium compound and lanthanon or transistion metal compound (Al/ metal) can about 1: about 200: 1 of 1-, about in other embodiments 2: about 150: 1 of 1-and about in other embodiments 5: 1-changed in about 100: 1.
The mol ratio of halogen contained compound and lanthanon or transistion metal compound is preferably described with the ratio (halogen/lanthanon or halogen/transition metal) of the mole number of lanthanon in the mole number of halogen atom in the halogen contained compound and lanthanon or the transistion metal compound or transition metal atoms.In one or more embodiments, halogen/lanthanon mol ratio can about 0.5: :-Yue 20: 1, about in other embodiments 1: about 10: 1 of 1-and about in other embodiments 2: 1-changed in about 6: 1.In one or more embodiments, halogen/transition metal mol ratio can about 0.5: about 100: 1 of 1-, about in other embodiments 1: about 60: 1 of 1-and about in other embodiments 3: 1-changed in about 40: 1.
In yet another embodiment; The mol ratio of non-coordination anion or non-coordination anion precursor and lanthanon or transistion metal compound (An/ metal) can about 0.5: about 20: 1 of 1-, about in other embodiments 0.75: about 10: 1 of 1-and about in other embodiments 1: 1-changed in about 6: 1.
Catalyst system can become to assign to form through combination or mixed catalyst.Although think that active catalyst species makes up from this, can't know interaction or the degree of reaction between various compositions or the component with any big degree of certainty.Therefore, the title complex of the various compositions that " catalyst system " cause with the simple mixtures that contains said composition, magnetism through physics or chemistry, the product or the aforesaid combination of said composition use a technical term.
The catalyst system that utilizes in the method disclosed herein can form through the whole bag of tricks.
In one embodiment, catalyst system can be through adding catalyst component in the solution that contains monomer and solvent or only original position formation in the bulk monomer with staged or simultaneous system.In one embodiment, can at first add alkylating agent, then be lanthanon or transistion metal compound, follow then, if you are using, halogen contained compound, or contain the compound or the non-coordination anion precursor of non-coordination anion.
In other embodiments, catalyst component can be approximately-20 ℃ of pre-mixings polymerization system outside to about 80 ℃ proper temperature, can the aging several minutes of gained catalyst system for some time of several days extremely be added to monomer solution with it then.
In yet another embodiment, catalyst system can form in the presence of at least a conjugate diene monomer in advance.That is to say that catalyst component can be approximately-20 ℃ of pre-mixings in the presence of a small amount of conjugate diene monomer to about 80 ℃ proper temperature.The amount that can be used for forming in advance the conjugate diene monomer of catalyst system can be about 1 to about 500 moles based on every mole of lanthanon or transistion metal compound; It is about 5 to about 250 moles and be about 10 to about 100 moles scope based on every mole of lanthanon or transistion metal compound in other embodiments based on every mole of lanthanon or transistion metal compound in other embodiments.Can the aging several minutes of gained catalyst system for some time to several days be added to then and want polymeric conjugate diene monomer residuum.
In yet another embodiment, catalyst system can form through using two stage steps.Fs can comprise alkylating agent and lanthanon or transistion metal compound under the situation that does not have conjugate diene monomer, or at a small amount of conjugate diene monomer down, extremely makes up under about 80 ℃ proper temperature can be approximately-20 ℃.In subordinate phase, can above-mentioned reaction mixture and halogen contained compound, non-coordination anion or non-coordination anion precursor be loaded to staged or simultaneous system and want polymeric conjugate diene monomer residuum.
When the solution of catalyst system solution or more than one catalyst components such as above-mentioned method is said when outside polymerization system, preparing, can be with an organic solvent or carrier.Organic solvent can be used for catalyst-solvent system or composition, or this solvent can only serve as catalyst system or the composition carrier wherein that can suspend.Organic solvent can be to the catalyst system inert.Useful solvent comprises hydro carbons flux such as aromatic hydrocarbon, aliphatic hydroxyl and clicyclic hydrocarbon.The limiting examples of aromatic hydrocarbon solvent comprises benzene,toluene,xylene, ethylbenzene, diethylbenzene and sym-trimethylbenzene etc.The limiting examples of aliphatic hydrocarbon solvent comprises Skellysolve A, normal hexane, normal heptane, octane, positive nonane, n-decane, iso-pentane, isohexane, iso-pentane, octane-iso, 2,2-dimethylbutane, sherwood oil, kerosene and white spirit wet goods.In addition, the limiting examples of clicyclic hydrocarbon flux comprises pentamethylene, hexanaphthene, methylcyclopentane and methyl cyclohexanol etc.Also can use the mixture that is purchased of above-mentioned hydro carbons.
The production of polymkeric substance can be accomplished with cyclic conjugated diene monomer through polymerization in the presence of the aforementioned catalyst system of catalytically effective amount is acyclic.The catalyzer total concn that in polymer material (polymerization mass), will use can depend on purity, the polymerization temperature of various factors such as composition, rate of polymerization and transformation efficiency, the molecular weight of expectation and the influencing each other of many other factorses of expectation.Therefore, the concrete total concn of catalyzer can not be set with limiting, only say each catalyst component that can use catalytically effective amount.In one or more embodiments; The usage quantity of lanthanon or transistion metal compound can be the about 2mmol of about 0.01-based on every 100g conjugate diene monomer, and about 1mmol of about in other embodiments 0.02-and the about 0.5mmol of about in other embodiments 0.05-change.
Polymerization can be carried out in as the organic solvent of thinner.In one embodiment, can use solution polymerization system, this solution polymerization system is to want the polymkeric substance of monomer polymerized and formation to dissolve in the system of polymerisation medium.Selectively, be insoluble to solvent wherein, can use the precipitation polymerization system through the polymkeric substance of selecting to form.Under both of these case, monomer polymerized can be in phase (condensed phase) with fixed attention.In addition, catalyst component solubilized or be suspended within the organic solvent.In these or other embodiment, catalyst component or component are not carried or are not immersed on the support of the catalyst.In other embodiments, can bearing catalyst composition or component.
In carrying out these polymerizations, can the amount of the organic solvent except the amount of the organic solvent that can be used for preparing catalyst system be added into polymerization system.Extra organic solvent can be same or different from the organic solvent that is used to prepare catalyst system.Can select with respect to the catalyst system that is used for catalyzed polymerization is organic solvent inert.Below illustrated exemplary hydro carbons flux.When using solvent, the concentration of monomer polymerized can be not limited to special scope.Yet; In one or more embodiments; The monomer concentration that when polymerization begins, is present in the polymerisation medium can be at the about 80 weight % of about 3 weight %-, in the scope of about 50 weight % of about in other embodiments 5 weight %-and the about 30 weight % of about in other embodiments 10 weight %-.
The polymerization of conjugated diolefine also can be carried out through mass polymerization, and said mass polymerization refers to not use in fact the polymerization environment of solvent.Mass polymerization can or be carried out in gas phase in concentrating liquid phase.
The polymerization of conjugated diolefine can be carried out with interrupter method, continuous processing or semi-continuous process.In semi-continuous process, monomer can be to substitute monomer polymerized as required and pack into off and on.Under any circumstance, can be under carry out polymerization under along with gentleness to vigorous stirring through the oxygen free condition that uses inert protective gas such as nitrogen, argon or helium.Polymerization temperature can from low temperature as below-10 ℃ to high temperature as changing widely more than 100 ℃.In one embodiment, polymerization temperature can be about 20 ℃ to about 90 ℃.Can pass through the externally cooled reactor jacket of thermal control (for example, with), inner cooling (reflux exchanger that for example, is connected to reactor drum through use is by the evaporation of monomer or solvent and concentrate) or the combination of these two kinds of methods and remove heat of polymerization.Although the polymerization pressure that uses can change widely, can keep about 1 normal atmosphere to about 10 atmospheric pressure ranges.
In case reach the transformation efficiency of expectation, can be through adding quencher to polyblend so that catalyst deactivation stops polymerization.Quencher can comprise proton compound, and it includes but not limited to alcohol, carboxylic acid, mineral acid, water or its mixture.Inhibitor such as 2,6 di tert butyl 4 methyl phenol can add, before or after quencher adds, add with adding quencher.The usage quantity of inhibitor can be in the scope of 0.2 weight %-1 weight % of polymer product.
When quencher polyblend, polymer product can reclaim from polyblend through utilizing any conventional steps of desolventizing as known in the art and exsiccant.For example, can through polymer paste is carried out the steam desolventizing then in the hot blast tunnel dry resulting polymers chip reclaim polymkeric substance.Selectively, can reclaim polymkeric substance through convection drying polymer paste on rotary drum dryer.The content of volatile matter can be lower than 1 weight % of polymkeric substance in the exsiccant polymkeric substance, is lower than 0.5 weight % in other embodiments.
Described herein gathering, (ring-type/acyclic) diene copolymers was as being 40 through using gel permeation chromatography (GPC) with the number-average molecular weight (Mn) of polyhutadiene standard test, 000-300,000, in other embodiments 50,000-150,000.In one or more embodiments, the MWD of these polymkeric substance (Mw/Mn) (also being known as " polydispersity index ") can be less than 5 to greater than 2.
Described herein gathering (ring-type/acyclic) diene copolymers cis-1, the 4-linkage content is greater than 60%, in other embodiments greater than 75%, in other embodiments greater than 92% with in other embodiments greater than 95%.Cis-1, the 4-linkage content can be measured through infrared spectroscopy.
Described herein gathering, the acyclic conjugate diene monomer content of (ring-type/acyclic) diene copolymers can be greater than 70%, in other embodiments greater than 90%.
Disclosed herein gathering, (ring-type/acyclic) diene copolymers was useful especially during tyre assembly in preparation.These tyre assemblies can use with the preparation rubber combination through independent use polymkeric substance disclosed herein or with rubbery polymer (rubber compounding thing) and prepare.The rubbery polymer of other that can use with (ring-type/acyclic) diene copolymers of disclosed herein gathering comprises natural elastomer and synthetic elastomer.Synthetic elastomer is usually from the polymerization of acyclic conjugate diene monomer.These acyclic conjugate diene monomers can with other monomer such as vinyl aromatic monomers copolymerization.Other rubbery polymer can be from the polymerization of ethene and more than one terminal olefins and more than one diene monomers of choosing wantonly.
Being used to prepare here, the rubber combination of the tyre assembly of record can comprise at least a rubber compounding thing and at least a multipolymer; Said at least a multipolymer comprises at least a cyclic conjugated diene monomer and at least a acyclic conjugate diene monomer; Wherein said at least a multipolymer comprises at least 90% acyclic conjugate diene monomer, has 50,000 to 150; 000 number-average molecular weight, and have at least 92% cis linkage content.In one embodiment, rubber combination comprises umber (parts-per-hundred-rubber) at least a multipolymer (phr) of at least 30 each hundred parts of rubber.In other embodiments, rubber combination comprises 40 to 60phr at least a multipolymer.
Available rubber compounding thing comprises tree elastomer; Synthetic polyisoprenes; Polyhutadiene; Polyisobutene-co-isoprene; X 050; Styrene-butadiene copolymer (solution and/or letex polymerization); Gather (ethene-co-propylene); Gather (vinylbenzene-co-divinyl); Gather (vinylbenzene-co-isoprene) and gather (vinylbenzene-co-isoprene-co-divinyl); Gather (isoprene-co-divinyl); Gather (ethene-co-propylene-co-diene); Thiorubber; Acrylic rubber; Urethanes; Silicone rubber; Epichloro hydrin rubber and composition thereof.These elastomericss can have a large amount of macromolecular structures that comprise linearity, branching and star.Normally used other composition also can be added into rubber combination in the rubber compounding.
Rubber combination can randomly comprise filler such as inorganic and organic filler.Organic filler comprises carbon black and starch.Mineral filler can comprise silicon-dioxide, white lake, Marinco H, clay (hydrated aluminium silicate salt) and composition thereof.
A large amount of rubber solidifying agent be can use, sulphur or peroxide curing system comprised.Solidifying agent is at Kirk-Othmer, ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, the 30th volume; 365-468 page or leaf (the nineteen eighty-two third edition), particularly Vulcanization Agents and Auxiliary Materials, the 390-402 page or leaf; And A.Y.Coran, Vulcanization, ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING; Record is introduced into for referencial use at this in (second edition in 1989).Vulcanizing agent can be used alone or in combination.In one or more embodiments, the influence that the formation of vulcanizable preparation of compositions and tire and curing are not implemented by the present invention.
Spendable other composition comprises promotor, oil, wax, incipient scorch suppressor factor, processing aid, zinc oxide, tackifying resin, reinforced resin, lipid acid such as Triple Pressed Stearic Acid, peptizer and more than one extra rubber.
These rubber combinations can be used for forming tyre assembly, and it includes but not limited to tyre surface, sidewall and housing unit (for example, carcass cord crust, tyre bead filler) etc.Preferably, gather (ring-type/acyclic) diene copolymers and be used for sidewall or housing unit prescription.In one or more embodiments, these prescriptions can comprise 30phr at least, in other embodiments 40 to 60phr gather (ring-type/acyclic) diene copolymers.
In one or more embodiments, rubber combination can comprise that the initial masterbatch of rubber components and filler prepares (rubber components randomly comprises (ring-type/acyclic) diene copolymers of disclosed herein gathering) through formation.This initial masterbatch can mix to about 125 ℃ starting temperature at about 25 ℃, and outflow temperature is about 135 ℃ to about 180 ℃ simultaneously.For preventing scorching (being also referred to as incipient scorch), this initial masterbatch can be got rid of vulcanizing agent.In case process initial masterbatch, then vulcanizing agent can and be blended into initial masterbatch at low temperatures in the introducing of final blending stage, and this does not preferably cause sulfuration process.Randomly, extra mix stages is sometimes referred to as refining (remill) again, can adopt between the stage at masterbatch mix stages and final blending.The various compositions that comprise functionalized copolymers disclosed herein can add during these refine again.Rubber compounding technology used herein and additive be the known The Compounding and Vulcanization of Rubber that is disclosed in usually, among the in Rubber Technology (second edition in 1973).
Be applicable to the mixing condition and the also known USP 5,227 that is documented in of process of silica-filled tire formulation, 425,5,719,207,5,717,022 with European patent 890,606 in, at this it is all introduced with for referencial use.In one or more embodiments, under the occasion of silicon-dioxide as filler (separately or with other filler combination), coupling agent and/or screener can during mixing be added in the rubber compounding.Available coupling agent and screener are disclosed in USP 3,842, and 111,3,873,489,3,978,103,3,997,581,4,002; 594,5,580,919,5,583,245,5,663,396,5,674,932,5,684; 171,5,684,172,5,696,197,6,608,145,6,667,362,6,579; 949, in 6,590,017,6,525,118,6,342,552 and 6,683,135, be introduced into for referencial use at this.In one embodiment, initial masterbatch does not substantially exist under coupling agent and the screener through comprising that functionalized copolymers disclosed herein and silicon-dioxide prepare.
But be used for the occasion that tire is made at vulcanizate compositions, these compsns can be processed into tyre assembly according to the conventional tyre manufacturing technology that comprises standard rubbers shaping (shaping), moulding (molding) and curing technology.Typically, sulfuration is implemented through heating vulcanisable compound in mould; For example, it can be heated to about 140 to about 180 ℃.Curing or crosslinked rubber combination can be described as vulcanizate, and it is included as heat cured three-dimensional, polymeric network structure usually.Other composition like processing aid and filler, can spread all over the sulfurized network structure and homodisperse.Pneumatic tyre can be like USP 5,866, and the manufacturing of discussing in 171,5,876,527,5,931,211 and 5,971,046 is introduced into for referencial use at this.
Embodiment disclosed herein will be through being more readily understood with reference to following examples.Therefore certainly, conspicuous to those skilled in the art many other embodiments or explanation are arranged still, think that these embodiment are merely illustration purpose and provide, and should not be construed as the scope that limits claim by any way.
Embodiment
Synthesizing of embodiment 1-cis-1 (comparison polymer 1)
In with the drying bottle of nitrogen purging, add hexane and 1,3-butadiene (Bd)/hexane blend, obtain the solution of 300g 15.0% (weight %) B d in hexane.In this solution, pack into triisobutyl aluminium (TIBA) solution (0.68M, 1.35mL), nickel octoate (Ni [EHA] 2) (0.050M is 0.61mL) with the own alcoholate (BF of boron trifluoride for solution 3* C 6H 13OH) solution.This bottle is placed 80 ℃ of water-baths and rolled 1 hour.Then with containing 2, the Virahol reaction mixture of 6-two-tertiary butyl-4-methylphenol (BHT) so that catalyst deactivation solidify and stabilization of polymer.Polyhutadiene is dry under 120 ℃ in rotary drum dryer then, and its character is shown in Table 1.
Synthesizing of embodiment 2-cis-1 (comparison polymer 2)
Comparison polymer 2 is used with embodiment 1 similar process and is prepared.Polymerizing condition and resulting polymers character are listed in the table 1.
Embodiment 3-cis-1,4-gathers the synthetic of (Bd-co-CHD)
In drying bottle, add with nitrogen purging hexane (103.6g), 1,3-butadiene (Bd)/hexane blend (22.2%, 194.6g) and 1 (1.8g), obtain the solution of 300g 15.0% monomer in hexane.In this solution, pack into Bd blend (1.1g), TIBA solution (0.68M, 0.99mL), Ni [EHA] 2Solution (0.050M, 0.45mL) and BF 3* C 6H 13OH solution (the preparatory formation catalyzer that 1.0M, sequential system 0.81mL) get.This bottle is placed 65 ℃ of water-baths and rolled 2.5 hours.Then with containing 2, the Virahol reaction mixture of 6-two-tertiary butyl-4-methylphenol (BHT) so that catalyst deactivation solidify and stabilization of polymer.Then that resulting polymers (polymkeric substance 3) is dry under 120 ℃ in rotary drum dryer, its character is shown in Table 1.
Embodiment 4-cis-1,4-gathers the synthetic of (Bd-co-CHD)
Multipolymer uses the 3 similar process preparations with embodiment.Polymerizing condition and resulting polymers (polymkeric substance 4) character is listed in the table 1.
Embodiment 5-cis-1,4-gathers the synthetic of (Bd-co-CHD)
Multipolymer uses the 3 similar process preparations with embodiment.Polymerizing condition and resulting polymers (polymkeric substance 5) character is listed in the table 1.
Figure BDA00001686836800281
Rubber combination
The polymkeric substance that obtains among the embodiment 1-5 uses the black sidewall type batching compounding in the 300g mixing machine according to the prescription that is shown in table 2.
Figure BDA00001686836800291
Embodiment A-cis-l, 4-gathers the crack growth test of (Bd-co-CHD)
Polymkeric substance 3 (comprising 2.3wt%CHD) is with " diene polymerization matter sample " in the tabulation 2.Mooney viscosity is measured and is carried out according to ASTM D-1646-89.The blended rubber raw materials solidified 33 minutes down at 145 ℃.Through using MTS 810 elastomerics pilot systems, under 10% strain (40Hz pulse distortion) condition through 250 * l0 3Individual circulation (5 circulation/seconds) is measured Dc/Dn (each round-robin crack length) and is torn energy.Gained character is summarized in the table 3.
Embodiment B
Except using polymkeric substance 4 (comprising 3.5wt%CHD) to replace the polymkeric substance 3, the same with embodiment A.Gained character is summarized in the table 3.
Embodiment C
Except using polymkeric substance 5 (comprising 5.4wt%CHD) to replace the polymkeric substance 3, the same with embodiment A.Gained character is summarized in the table 3.
Embodiment D-relatively
Except using polymkeric substance 1 to replace the polymkeric substance 3, the same with embodiment A.Gained character is summarized in the table 3.
Embodiment E-comparison
Except using polymkeric substance 2 to replace the polymkeric substance 3, the same with embodiment A.Gained character is summarized in the table 3.
Figure BDA00001686836800301
As passing through shown in the table 3, to compare with contrasting NiBR, the CHD multipolymer has better anti-crack growth property.Even have the mooney viscosity suitable with E with embodiment D and tear energy, embodiment A, B and C also obtain better anti-crack growth property.In addition, Embodiment C (sample with the highest CHD content) shows best anti-crack growth property.
For the degree that uses a technical term in this specification sheets or claims " comprising ", its objective is " comprising " similarly mode with term and to comprise, because this term " comprises " or " comprising " is when in claim, using as the transition speech, to have explained.In addition, for term " or " use the degree of (for example, A or B), its objective is fingers " A or B perhaps the two ".When the applicant is intended to expression " have only A or B but do not have the two ", " have only A or B but do not have the two " then will use a technical term.Thereby, here term " or " use be the meaning that comprises, rather than do not comprise use.Referring to Bryan A, Garner, A Dictionary of Modern Legal Usage 624 (nineteen ninety-five second editions).In addition, for term " ... in " or " arrive ... in " degree of in this specification sheets or claims, using its objective is extra meaning " exist ... go up " or " arrive ... go up ".In addition, " connection " degree of in this specification sheets or claims, using its objective is not only to mean " being connected directly to " for term, but also means " being connected to indirectly ", as connecting through another assembly or a plurality of assembly.
Though this specification sheets is explained through the description of its embodiment, and though this embodiment describes in detail, the applicant's purpose is not to limit or limit by any way the scope of appended claims to this details.Extra advantage will be easy to occur to those skilled in the art with improving.Therefore, the illustrative example that the application is not limited to detail, typical equipments and illustrates and describe, but aspect widely.Therefore, under the situation of spirit that does not depart from the total invention idea of the applicant or scope, can change from this details.

Claims (20)

1. method of using polymerisation catalyst system to prepare the multipolymer of acyclic conjugated diolefine and cyclic conjugated diene, said method comprises:
Utilize at least a acyclic conjugate diene monomer of polymerisation catalyst system polymerization and at least a cyclic conjugated diene monomer, said polymerisation catalyst system comprises:
(a) transistion metal compound or lanthanide metal compound,
(b) alkylating agent; With
(c) inorganic halides alcoholate,
Wherein said multipolymer comprises at least 90% acyclic conjugate diene monomer, has 40,000 to 300,000 number-average molecular weight and has at least 92% cis linkage content.
2. method according to claim 1, wherein said multipolymer has 50,000 to 150,000 number-average molecular weight.
3. method according to claim 1, wherein said at least a acyclic conjugated diolefine is selected from by 1,3-butadiene, isoprene, 1; 3-pentadiene, 1,3-hexadiene, 2,3-dimethyl--l; 3-divinyl, 2-ethyl-l, 3-divinyl, 2-methyl isophthalic acid, 3-pentadiene, 3-methyl isophthalic acid; 3-pentadiene, 4-methyl isophthalic acid, 3-pentadiene and 2, the group that the 4-hexadiene is formed.
4. method according to claim 1, wherein said at least a cyclic conjugated diene are selected from by 1,1,1,3-cycloheptadiene and 1, the group that 3-cyclooctadiene and verivate thereof are formed.
5. method according to claim 1, wherein said polymerisation catalyst system comprises:
(a) be selected from the transistion metal compound of the group of forming by nickel, cobalt and palladium compound,
(b) alkylating agent; With
(c) inorganic halides alcoholate.
6. method according to claim 1, wherein said polymerisation catalyst system comprises:
(a) be selected from the lanthanide metal compound of the group of forming by lanthanum, samarium and neodymium compound,
(b) alkylating agent; With
(c) inorganic halides alcoholate.
7. method according to claim 5, wherein said transistion metal compound are selected from by nickel benzoate, nickelous acetate, nickel naphthenate, nickel octoate, neodecanoic acid nickel, two (α-Fu Nan dioxime) nickel, palmitinic acid nickel, nickel stearate, acetopyruvic acid nickel, salicylic aldehyde nickel, two (cyclopentadiene) nickel, two (salicylic aldehyde) second diimine nickel, cyclopentadienyl moiety-nitrosyl radical nickel, two (η 3-allyl group) nickel, two (π-ring suffering-1,5-diene) nickel, two (η 3-allyl group nickel trifluoro-acetate), the group of nickel tetracarbonyl, boron acidylate nickel, neodecanoic acid nickelous borate, caproic acid nickelous borate, naphthenic acid nickelous borate, Triple Pressed Stearic Acid nickelous borate, sad nickelous borate, 2 ethyl hexanoic acid nickelous borate and composition thereof composition.
8. method according to claim 1, the alcoholate of wherein said inorganic halides alcoholate partly comprise 4 to 20 carbon atoms.
9. method according to claim 1, wherein said inorganic halides alcoholate is the boron trifluoride alcoholate.
10. method according to claim 1, wherein said alkylating agent are to have formula AlR nX 3-nOrgano-aluminium compound; Each R that wherein can be identical or different is the unit price organic group that is connected to the aluminium atom via carbon atom; Each X that wherein can be identical or different be Wasserstoffatoms, carboxylic acid ester groups, alkoxide group or fragrant oxide groups and wherein n be the integer of 1-3.
11. method according to claim 1; Wherein through comprise said transistion metal compound or lanthanide metal compound mix with said alkylating agent, thereafter with said inorganic halides alcoholate method of mixing, at least a portion of said polymerisation catalyst system is pre-formed before the said monomer being added into.
12. method according to claim 1, wherein said multipolymer has the polydispersity index of 2-5.
13. method according to claim 1, wherein said multipolymer have at least 95% cis linkage content.
14. method according to claim 1, wherein said at least a acyclic conjugated diolefine is a 1,3-butadiene; Said at least a cyclic conjugated diene is 1; The 3-cyclohexadiene, said containing metal compound is a nickel octoate, said inorganic halides alcoholate is the own alcoholate of boron trifluoride; Said alkylating agent is that triisobutyl aluminium and wherein said multipolymer have the polydispersity index of 2-5 and have at least 95% cis linkage content.
15. a rubber combination, it comprises:
At least a multipolymer; Said multipolymer comprises at least a cyclic conjugated diene monomer and at least a acyclic conjugate diene monomer, and wherein said at least a multipolymer comprises at least 90% acyclic conjugate diene monomer, has 50; 000 to 150; 000 number-average molecular weight, and have at least 92% cis linkage content and
At least a rubber compounding thing.
16. rubber combination according to claim 15, it comprises 40 to 60phr said at least a multipolymer.
17. rubber combination according to claim 15, wherein said at least a rubber compounding thing is selected from the group of being made up of tree elastomer, TR 301, polyhutadiene and styrene-butadiene copolymer rubber.
18. a rubber combination, it comprises:
At least at least a multipolymer of processing through method according to claim 1 of 30phr and
Less than at least a rubber compounding thing of 70phr, wherein said at least a rubber compounding thing is selected from the group of being made up of tree elastomer, TR 301, polyhutadiene and styrene-butadiene copolymer rubber.
19. a rubber combination, it comprises:
At least at least a multipolymer of processing through method according to claim 14 of 30phr and
Less than at least a rubber compounding thing of 70phr, wherein said at least a rubber compounding thing is selected from the group of being made up of tree elastomer, TR 301, polyhutadiene and styrene-butadiene copolymer rubber.
20. a pneumatic tyre, it comprises:
Tread package, inside and outside sidewall components and housing unit, at least a assembly that wherein is selected from the group of being made up of inside and outside sidewall components and housing unit comprises the multipolymer of processing through method according to claim 1.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108002970A (en) * 2017-12-26 2018-05-08 濮阳盛华德化工有限公司 A kind of preparation method of 1,5- cyclo-octadiene
CN110256618A (en) * 2019-05-31 2019-09-20 宁波金海晨光化学股份有限公司 A kind of poly- pentadiene and its preparation method and application of cis- -1,4 structure
CN115109189A (en) * 2022-06-15 2022-09-27 宁夏清研高分子新材料有限公司 Preparation method of cycloolefin copolymer material, catalyst system and application thereof

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR112012008797A2 (en) * 2009-10-14 2020-09-15 Bridgestone Corporation processes for preparing cyclic and acyclic diene copolymer and rubber composition
US8598286B1 (en) 2012-11-05 2013-12-03 The Goodyear Tire & Rubber Company High cis diene/phenylbutadiene copolymers prepared using a Ziegler/Natta neodymium catalyst
US8816032B1 (en) 2013-05-24 2014-08-26 The Goodyear Tire & Rubber Company Copolymer of conjugated diene and 1-vinylcycloalkene
KR101656126B1 (en) * 2013-09-30 2016-09-08 주식회사 엘지화학 Novel neodymium compound and catalysts for polymerizing diene comprising the same
EP3156639A1 (en) 2015-10-15 2017-04-19 Continental Automotive GmbH Fuel injection valve with a weld ring and method for producing the same
US10066035B2 (en) * 2015-12-07 2018-09-04 Bridgestone Corporation Catalyst systems and methods for preparation of 1,4-polybutadiene rubber
US10919989B2 (en) * 2017-10-20 2021-02-16 Iowa State University Research Foundation, Inc. End group functionalization agents for polydiene
KR102193437B1 (en) * 2017-10-30 2020-12-21 주식회사 엘지화학 Method of preparation for catalyst for the polymerization of conjugated diene, catalyst prerared by the same method and method of preparation for modified conjugated diene polymer using the same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1294167A (en) * 1970-08-07 1972-10-25 Inst Neftechimicheskogo Sintez Stereospecific synthetic rubber based on 1,3-butadiene and method of producing same
US3723400A (en) * 1969-12-31 1973-03-27 I Garmonov Method of producing 1,4-cis-polybutadiene and cis-copolymers of butadiene
US4020251A (en) * 1974-02-27 1977-04-26 Phillips Petroleum Company 1,3-Cyclodiene-acyclic conjugated diene copolymers
GB2044277A (en) * 1979-02-19 1980-10-15 Sumitomo Chemical Co Process for producing a cyclopentadiene copolymer and a composition comprising said copolymer and a rubber

Family Cites Families (96)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE629111A (en) * 1962-03-03
US3297667A (en) 1963-02-28 1967-01-10 Union Carbide Corp Production of cis-1, 4-polydienes by polymerization of 1, 3-dienes
US3541063A (en) 1967-12-29 1970-11-17 Goodyear Tire & Rubber Process for the polymerization of diolefins with a catalyst comprising alkylaluminum compounds,group iii-b organo metal compounds and organoaluminum fluoride compounds
US3740382A (en) 1969-12-31 1973-06-19 S Beilin Stereospecific synthetic rubber based on 1,3-butadiene and method of producing same
US3873489A (en) 1971-08-17 1975-03-25 Degussa Rubber compositions containing silica and an organosilane
US3978103A (en) 1971-08-17 1976-08-31 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Sulfur containing organosilicon compounds
BE787691A (en) 1971-08-17 1973-02-19 Degussa ORGANOSILICIC COMPOUNDS CONTAINING SULFUR
US3794604A (en) 1971-09-24 1974-02-26 Goodyear Tire & Rubber Diolefin polymerization catalyst composition
SU580840A3 (en) 1974-02-07 1977-11-15 Дегусса (Фирма) Method of preparing sulfur-containing silicones
US4127710A (en) 1974-10-02 1978-11-28 Phillips Petroleum Company Copolymerization of a 1,3-cyclodiene and a linear conjugated diene
US4002594A (en) 1975-07-08 1977-01-11 Ppg Industries, Inc. Scorch retardants for rubber reinforced with siliceous pigment and mercapto-type coupling agent
US4223116A (en) 1976-06-17 1980-09-16 Phillips Petroleum Company Conjugated diene polymerization process and catalyst
US4113930A (en) 1976-08-02 1978-09-12 Phillips Petroleum Company Hydrogenated 1,3-cyclohexadiene/1,3-butadiene copolymers
US4138536A (en) 1976-12-20 1979-02-06 Phillips Petroleum Company Polymerization of 1,3-cyclodiene with vinylaromatic hydrocarbon
US4107081A (en) 1977-06-24 1978-08-15 The Firestone Tire & Rubber Company Catalyst system and process for polymerization of conjugated dienes therewith
US4174431A (en) 1977-11-07 1979-11-13 The Firestone Tire & Rubber Company Process for polymerizing conjugated dienes
JPS55104306A (en) * 1979-02-06 1980-08-09 Sumitomo Chem Co Ltd Production of cyclopentadiene copolymer resin
JPS55104307A (en) * 1979-02-06 1980-08-09 Sumitomo Chem Co Ltd Production of cyclopentadiene resin and copolymer resin
US4248988A (en) 1979-10-18 1981-02-03 The Firestone Tire & Rubber Company Process for the preparation of cyclized polymeric dienes
US4264753A (en) 1979-10-18 1981-04-28 The Firestone Tire & Rubber Company Process for polymerizing conjugated dienes
CA1223396A (en) 1981-06-29 1987-06-23 Tooru Shibata Process for producing conjugated diene polymer
IT1140452B (en) 1981-09-25 1986-09-24 Anic Spa PROCEDURE FOR THE POLYMERIZATION OF CONJUGATED DIOLEFINS AND MEDIA SUITABLE FOR THE PURPOSE
US4522988A (en) 1984-06-04 1985-06-11 The Firestone Tire & Rubber Company Method of preparing high cis-1,4 diene polymers having good green strength and tack
US4520123A (en) 1984-07-02 1985-05-28 The Firestone Tire & Rubber Company Catalyst system and process for polymerizing conjugated dienes
US4591624A (en) 1984-07-02 1986-05-27 The Firestone Tire & Rubber Company Catalyst system and process for polymerizing conjugated dienes
IT1186747B (en) 1985-07-01 1987-12-16 Enichem Elastomers IMPROVED PROCEDURE FOR POLYMERIZATION OR COPOLYMERIZATION OF BUTADIENE
US5064910A (en) 1986-09-05 1991-11-12 Japan Synthetic Rubber Co., Ltd. Preparation of conjugated diene polymers modified with an organo-tin or germanium halide
GB8830007D0 (en) 1988-12-22 1989-02-15 Enichem Elastomers Polymerization of butadiene
SU1705305A1 (en) * 1989-07-03 1992-01-15 Ярославский Научно-Исследовательский Институт Мономеров Для Синтетического Каучука Method of producing polymers based on cyclopentadiene
US5260370A (en) 1990-09-21 1993-11-09 Bridgestone Corporation Oil extended ultra high molecular weight elastomers
US5231152A (en) 1990-12-18 1993-07-27 Bridgestone Corporation Continuous process for preparing copolymers of conjugated dienes and aromatic vinyl compounds
FR2673187B1 (en) 1991-02-25 1994-07-01 Michelin & Cie RUBBER COMPOSITION AND TIRE COVERS BASED ON SAID COMPOSITION.
CA2077370C (en) 1991-09-03 1998-12-15 James E. Hall Dispersion copolymers in linear aliphatic solvents
JP3207502B2 (en) 1992-04-20 2001-09-10 株式会社ブリヂストン Method for producing copolymer
US5248722A (en) 1992-06-02 1993-09-28 Bridgestone Corporation Tire tread composition
DE69434471D1 (en) * 1993-05-21 2005-09-29 Asahi Chemical Ind CYCLICALLY CONJUGATED DIEN POLYMER
JP3141190B2 (en) 1993-05-21 2001-03-05 旭化成株式会社 Cyclic conjugated diene copolymer
JP3101151B2 (en) 1993-05-21 2000-10-23 旭化成工業株式会社 Cyclic conjugated diene polymer and polymerization method thereof
JP3441015B2 (en) 1993-06-16 2003-08-25 旭化成株式会社 Novel polymers containing saturated cyclic molecular structural units
JP3769294B2 (en) 1993-07-30 2006-04-19 日本ゼオン株式会社 Modified conjugated diene polymer, production method thereof and composition thereof
US5428119A (en) 1993-11-09 1995-06-27 Polysar Rubber Corporation Process for polybutadiene production using catalyst with high activity
US5508336A (en) 1993-12-29 1996-04-16 Bridgestone Corporation Rubber composition
US6300451B1 (en) 1994-10-24 2001-10-09 Exxon Chemical Patents Inc. Long-chain branched polymers and their production
US5580919A (en) 1995-03-14 1996-12-03 The Goodyear Tire & Rubber Company Silica reinforced rubber composition and use in tires
US5674932A (en) 1995-03-14 1997-10-07 The Goodyear Tire & Rubber Company Silica reinforced rubber composition and use in tires
JP3555809B2 (en) 1995-06-19 2004-08-18 株式会社ブリヂストン Radial tire
AT405285B (en) 1995-09-07 1999-06-25 Semperit Ag RUBBER BLEND
US5583245A (en) 1996-03-06 1996-12-10 The Goodyear Tire & Rubber Company Preparation of sulfur-containing organosilicon compounds
US5719207A (en) 1996-03-18 1998-02-17 The Goodyear Tire & Rubber Company Silica reinforced rubber composition and tire with tread
US5696197A (en) 1996-06-21 1997-12-09 The Goodyear Tire & Rubber Company Heterogeneous silica carbon black-filled rubber compound
JP3606411B2 (en) 1996-07-10 2005-01-05 株式会社ブリヂストン Tire vulcanization mold and manufacturing method thereof
JP3117645B2 (en) 1996-09-03 2000-12-18 株式会社ブリヂストン Pneumatic radial tire
US5663396A (en) 1996-10-31 1997-09-02 The Goodyear Tire & Rubber Company Preparation of sulfur-containing organosilicon compounds
US5684172A (en) 1997-02-11 1997-11-04 The Goodyear Tire & Rubber Company Process for the preparation of organosilicon polysulfide compounds
US5684171A (en) 1997-02-11 1997-11-04 The Goodyear Tire & Rubber Company Process for the preparation of organosilicon polysulfide compounds
US6221943B1 (en) 1997-07-11 2001-04-24 Bridgestone Corporation Processability of silica-filled rubber stocks
US6525118B2 (en) 1997-07-11 2003-02-25 Bridgestone Corporation Processability of silica-filled rubber stocks with reduced hysteresis
US6384117B1 (en) 1997-07-11 2002-05-07 Bridgestone Corporation Processability of silica-filled rubber stocks
AU8917998A (en) 1997-08-21 1999-03-08 Crompton Corporation Blocked mercaptosilane coupling agents for filled rubbers
US5971046A (en) 1997-09-17 1999-10-26 Bridgestone/Firestone, Inc. Method and apparatus for bonding an active tag to a patch and a tire
JP3334650B2 (en) * 1998-05-08 2002-10-15 株式会社豊田中央研究所 Cyclic conjugated diene polymer and polymerization method thereof
US6399732B2 (en) 1998-10-14 2002-06-04 Bridgestone Corporation Preparation of conjugated diene polymers by using an iron-based catalayst system
US6211313B1 (en) 1999-11-12 2001-04-03 Bridgestone Corporation Iron-based catalyst composition and process for producing conjugated diene polymers
US6977281B1 (en) 1999-11-12 2005-12-20 Bridgestone Corporation Modified polymers prepared with lanthanide-based catalysts
EP1099711B1 (en) 1999-11-12 2006-03-29 JSR Corporation Modified conjugated diene polymer, method of producing it and rubber composition comprising the same
US6992147B1 (en) 1999-11-12 2006-01-31 Bridgestone Corporation Modified polymers prepared with lanthanide-based catalysts
FR2802542A1 (en) 1999-12-20 2001-06-22 Michelin Soc Tech VULCANIZABLE RUBBER COMPOSITION FOR THE MANUFACTURE OF A PNEUMATIC AND PNEUMATIC TIRE WHERE THE TREAD BAND INCLUDES SUCH A COMPOSITION
US6288183B1 (en) 1999-12-30 2001-09-11 Bridgestone Corporation Catalyst composition and process for controlling the characteristics of conjugated diene polymers
US6765066B2 (en) 1999-12-30 2004-07-20 Bridgestone Corporation Copolymers prepared by using both anionic polymerization techniques and coordination catalysts
US6160063A (en) 1999-12-30 2000-12-12 Bridgestone Corporation Iron-based catalyst for producing binary cis-1,4-/1,2-polybutadiene
US6348550B1 (en) 2000-04-13 2002-02-19 Bridgestone Corporation Molybdenum-based catalyst composition and process for controlling the characteristics of conjugated diene polymers
JP4342690B2 (en) * 2000-04-20 2009-10-14 宇部興産株式会社 Process for producing modified polybutadiene, modified polybutadiene, and rubber composition
US6590017B1 (en) 2000-05-15 2003-07-08 Bridgestone Corporation Processability of silica-reinforced rubber containing an amide compound
US6608145B1 (en) 2000-10-13 2003-08-19 Bridgestone Corporation Silica-reinforced rubber compounded with an organosilane tetrasulfide silica coupling agent at high mixing temperature
US6627712B2 (en) 2001-02-19 2003-09-30 Bridgestone Corporation Manufacture of conjugated diene polymers by using an iron-based catalyst composition
US6465585B2 (en) 2001-02-19 2002-10-15 Bridgestone Corporation Chromium-based catalyst composition for producing conjugated diene polymers
WO2002068484A1 (en) 2001-02-28 2002-09-06 Bridgestone Corporation Continuous process for the production of conjugated diene polymers having narrow molecular weight distribution and products therefrom
US6320004B1 (en) 2001-04-05 2001-11-20 Bridgestone Corporation Manufacture of conjugated diene polymers by using an iron-based catalyst composition
JP4197493B2 (en) 2001-08-17 2008-12-17 旭化成株式会社 Cyclic conjugated diene copolymer
DE60224963T2 (en) 2001-09-13 2009-03-05 Jsr Corp. Cyclic olefin addition copolymer and process for its preparation, crosslinkable composition, crosslinked product and process for its preparation and optically transparent material and its application
US6579949B1 (en) 2001-10-30 2003-06-17 Bridgestone Corporation Preparation of low hysteresis rubber by reacting a lithium polymer with a sulfur containing reagent
US20040242780A1 (en) 2001-11-05 2004-12-02 Christine Rademacher Process for producing blends of syndiotactic, 1,2-polybutadiene and rubbery elastomers
US6699813B2 (en) 2001-11-07 2004-03-02 Bridgestone Corporation Lanthanide-based catalyst composition for the manufacture of polydienes
US6699941B1 (en) 2002-11-07 2004-03-02 Kraton Polymers U.S. Llc Block copolymer
JP4240209B2 (en) 2003-05-21 2009-03-18 Ｊｓｒ株式会社 Modified conjugated diene polymer, production method thereof and composition containing the same
US7094849B2 (en) 2003-12-15 2006-08-22 Bridgestone Corporation Bulk polymerization process for producing polydienes
US7442748B2 (en) 2004-03-01 2008-10-28 Bridgestone Corporation Continuous polymerization reactor
CN100564407C (en) 2004-03-02 2009-12-02 株式会社普利司通 Bulk polymerization
KR101344592B1 (en) 2004-07-02 2013-12-26 도꾸리쯔교세이호징 리가가쿠 겐큐소 Polymerization catalyst compositions containing metallocene complexes and polymers produced by using the same
JP4901101B2 (en) 2004-12-28 2012-03-21 株式会社ブリヂストン Modified polymer, rubber composition and tire
US7585805B2 (en) 2005-11-22 2009-09-08 Bridgestone Corporation Nickel-based catalyst composition
US7671138B2 (en) 2006-05-26 2010-03-02 Bridgestone Corporation Polymers functionized with hydrobenzamides
US7732534B2 (en) 2006-08-28 2010-06-08 Bridgestone Corporation Polymers functionalized with nitro compounds
US20080051519A1 (en) 2006-08-28 2008-02-28 Steven Luo Polymers functionalized with nitro compounds
US7820580B2 (en) * 2007-11-15 2010-10-26 Bridgestone Corporation Nickel-based catalysts for preparing high cis 1,4-polydienes
BR112012008797A2 (en) * 2009-10-14 2020-09-15 Bridgestone Corporation processes for preparing cyclic and acyclic diene copolymer and rubber composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3723400A (en) * 1969-12-31 1973-03-27 I Garmonov Method of producing 1,4-cis-polybutadiene and cis-copolymers of butadiene
GB1294167A (en) * 1970-08-07 1972-10-25 Inst Neftechimicheskogo Sintez Stereospecific synthetic rubber based on 1,3-butadiene and method of producing same
US4020251A (en) * 1974-02-27 1977-04-26 Phillips Petroleum Company 1,3-Cyclodiene-acyclic conjugated diene copolymers
GB2044277A (en) * 1979-02-19 1980-10-15 Sumitomo Chemical Co Process for producing a cyclopentadiene copolymer and a composition comprising said copolymer and a rubber

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108002970A (en) * 2017-12-26 2018-05-08 濮阳盛华德化工有限公司 A kind of preparation method of 1,5- cyclo-octadiene
CN110256618A (en) * 2019-05-31 2019-09-20 宁波金海晨光化学股份有限公司 A kind of poly- pentadiene and its preparation method and application of cis- -1,4 structure
CN115109189A (en) * 2022-06-15 2022-09-27 宁夏清研高分子新材料有限公司 Preparation method of cycloolefin copolymer material, catalyst system and application thereof
CN115109189B (en) * 2022-06-15 2024-01-30 宁夏清研高分子新材料有限公司 Preparation method of cycloolefin copolymer material, catalyst system and application thereof

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